CN101273077B - Crosslinking method - Google Patents
Crosslinking method Download PDFInfo
- Publication number
- CN101273077B CN101273077B CN2006800242292A CN200680024229A CN101273077B CN 101273077 B CN101273077 B CN 101273077B CN 2006800242292 A CN2006800242292 A CN 2006800242292A CN 200680024229 A CN200680024229 A CN 200680024229A CN 101273077 B CN101273077 B CN 101273077B
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- CN
- China
- Prior art keywords
- branching
- oil
- metathesis
- acyclic
- polymkeric substance
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
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- 238000000034 method Methods 0.000 title claims abstract description 78
- 238000004132 cross linking Methods 0.000 title description 21
- 239000000178 monomer Substances 0.000 claims abstract description 118
- 238000005649 metathesis reaction Methods 0.000 claims abstract description 75
- 125000002015 acyclic group Chemical group 0.000 claims abstract description 59
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 42
- 239000000126 substance Substances 0.000 claims description 76
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- 150000001875 compounds Chemical class 0.000 claims description 41
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- 239000000853 adhesive Substances 0.000 claims description 14
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- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid group Chemical group C(CCCCCCC\C=C/CCCCCCCC)(=O)O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 3
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- PHYFQTYBJUILEZ-UHFFFAOYSA-N Trioleoylglycerol Natural products CCCCCCCCC=CCCCCCCCC(=O)OCC(OC(=O)CCCCCCCC=CCCCCCCCC)COC(=O)CCCCCCCC=CCCCCCCCC PHYFQTYBJUILEZ-UHFFFAOYSA-N 0.000 description 2
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D165/00—Coating compositions based on macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Coating compositions based on derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/333—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
- C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
Abstract
The invention provides a method of preparing a crosslinked polymer, which method comprises polymerising branched polyunsaturated monomers by a metathesis polymerisation reaction, wherein the branched polyunsaturated monomers contain acyclic ethylenically unsaturated groups that are capable of undergoing polymerisation by a metathesis reaction such that the metathesis polymerisation produces a crosslinked polymer and substantially no non-volatile ethylenically unsaturated by-products.
Description
Technical field
The present invention relates to prepare the method for crosslinked polymkeric substance, and by the crosslinked polymkeric substance of this method preparation.The invention still further relates to can be according to the crosslinked precursor composition of this method, and the method that is used to prepare the compound that can be used for preparing this crosslinked polymkeric substance.The described method that is used to prepare crosslinked polymkeric substance is particularly useful for polymer-based carbon coating and adhesive application, therefore, can describe the present invention easily hereinafter with reference to these application.However, it should be understood that this method also can be used for other application.
Background technology
Crosslinked polymkeric substance usually can polymer chain network be feature, wherein at least some chains connect by bridged group.The character of bridging can produce very big change, forms ways of connecting because it can be bridged group and polymer chain.The quantity of the bridged group that exists in the crosslinked polymkeric substance, very big change also can take place with the change (because crosslinked degree increases in the polymkeric substance) of effective molecular weight, viscosity and the solubleness of polymkeric substance in promptly crosslinked degree.Having arbitrarily, the polymkeric substance of big crosslinking degree is insoluble in the solvent usually basically.
Compare with its not crosslinked counterpart, crosslinked polymkeric substance demonstrates superior physical and mechanical property usually.Therefore, the performance of polymer-based carbon coating and tackiness agent (that is, lacquer, tackiness agent, filler, priming paint and sealing agent etc.) also can be improved by these products with crosslinked polymer architecture are provided usually.But because its crosslinked polymer architecture, crosslinked polymkeric substance can't be applied on the base material with most of coating and the required mode of adhesive application usually.Specifically, crosslinked polymkeric substance can't be molded as required shape usually or be applied to stratiform on the surface of base material.
For polymer-based carbon coating and the tackiness agent that has crosslinked structure and be easy to be applied to the performance on the base material is provided, make such product usually, make after being applied to this product on the base material, produce crosslinked.Be used to realize that this applies one of crosslinked prevailing blending process in back and provides at least a product that contains the polymkeric substance of reactive functional groups.Described reactive functional groups provides and can react and promote the back crosslinked site of applying of product.
A kind of method that this product with these reactive functional groups is provided is that product is mixed with have undersaturated natural oil (for example, glyceride oil), the perhaps Synolac that is formed by undersaturated natural oil.In the coating that use in the whole world, account for very big per-cent with these material composition prepared, be called as air-dry enamel or oil base coating at large.These lacquers dry or to solidify mainly be because oxygen in the atmosphere and the ethylenic unsaturated group reaction that derives from described oil, it has promoted to be called as the crosslinked of composition in the method for autoxidation.
But although forming aspect the crosslinked polymer architecture effectively, the autoxidation method is very slow.After with the film dried overnight, just can apply required enough crosslinked of second layer lacquer and do not destroy the first layer lacquer.Even like this, some environmental factorss such as temperature and humidity also can postpone exsiccant speed.
The method of autoxidation also can continue long period of time (that is, in the dry back of lacquer), and can cause the physicals of paint film to descend.This decline can limit the performance of described coating, especially externally in the environment.Oil base coating also can flavescence under non-sunlight direct projection.The various atmosphere radical reactions of the remaining unsaturated group of the lipid acid section that these lacquers have the trend of flavescence to be considered to come to derive from polymkeric substance.
The another kind of method that this product with these reactive functional groups is provided is it to be mixed with have the polymkeric substance that contains the functional group of reacting with water.In this case, described product can apply the crosslinked structure in back by being exposed to form under the atmospheric moisture.But, because its inherent moisture sensitive needs exactissima diligentia to get rid of moisture in manufacturing, packing and the storage process of product.Although noted getting rid of moisture from product, the moisture-curable product has limited shelf life usually.
Coating and tackiness agent provide with two parts of formulas usually, and a copy of it comprises the polymkeric substance that contains functional group, described functional group can with the functional group reactions of the polymkeric substance that comprises in another part.In this case, each part was all mixed before applying, and applied the back by being reflected at of functional group that each part provided and take place crosslinked.Described two parts of formula coating and binder formulation have usually the insensitive advantage of moisture, therefore have usually good shelf life.But because its reactivity, each component can not provide with the form of single type composition, because such most convenient.In addition, when mixing for two parts, product must use in the short time period.
Apply the crosslinked polymer architecture in back though aforementioned moisture-curable and two parts of formula coating and adhesive product can form effectively, the reactive functional groups that is used to provide crosslink sites can be given product toxicity.For example, the reactive functional groups that generally is used for these products comprises isocyanic ester, amine, epoxide and cyanoacrylate.Therefore, in the manufacturing of these products and use, can produce the danger relevant with Occupational Health and Safety.In addition, the monomer that comprises the reactive functional groups that is used for these products is normally expensive.
Be used for realizing applying the product that the crosslinked another kind of general blending process in back provides two parts of types, a copy of it contains the group initiator, and another part is contained crosslinkable polymer composition.In this case, described initiator mixed with polymeric constituent before applying, and then immediately mixture was applied on the base material usually, and produced crosslinked after applying by the crosslinking reaction that is caused by the promoted group of initiator.Use aforementioned blending process, this technology also provides and has realized applying the crosslinked effective means in back.But this polymer composition can be precocious and spontaneously crosslinked, and this method is that exothermicity is very large, and the possibility of blast is arranged.Therefore, these polymer compositions usually need be with the inhibitor preparation to prevent the generation of above-mentioned situation.Although used inhibitor, described polymer composition has limited shelf life usually.In addition, generally be used for the initiator of these products, for example contain those of peroxide bond, Nitrosamines normally, there is the possibility of blast in itself.
Therefore, still need to provide another kind to be used to prepare the method for crosslinked polymkeric substance, this method can overcome or be reduced by at least some shortcomings relevant with preceding method.
Summary of the invention
The invention provides a kind of method for preparing crosslinked polymkeric substance, this method comprises by metathesis polymerization reacts the many unsaturated monomers of polymerization branching, wherein, the many unsaturated monomers of described branching comprise and can carry out the acyclic ethylenic unsaturated group of polymeric by metathesis reaction, make this metathesis polymerization can produce crosslinked polymkeric substance, and do not have the unsaturated by product of nonvolatile ethylenic basically.
Usually, the many unsaturated monomers of alleged herein branching comprise on it atom or nuclear that connects at least three parts, and in them at least three are contained one or morely can carry out the acyclic ethylenic unsaturated group of polymeric by metathesis reaction.
Have been found that the many unsaturated monomers of branching can provide crosslinked polymer architecture by the polymerization of transposition path.Method of the present invention is particularly useful for making the crosslinked polymkeric substance that can be used for polymer-based carbon coating and tackiness agent, and can easily be used to provide apply the back crosslinked (post-application crosslinking).
As hereinafter will be described herein in more detail, the many unsaturated monomers of described branching also can with other unsaturated monomer such as diene monomers polymerization.
It will be understood to those of skill in the art that metathesis polymerization reaction provides polymeric articles and as the ethylenically unsaturated compounds of by product.When forming crosslinked polymkeric substance of the present invention, importantly metathesis polymerization has realized not having basically the unsaturated by product of nonvolatile ethylenic.In other words, except crosslinked polymkeric substance, the by product of all basically metathesis polymerizations is the unsaturated by product of volatile ethylenic.As volatile, the unsaturated by product of described ethylenic can more easily separate with reaction mixture.This has not only promoted the formation of crosslinked polymkeric substance, makes advantageously also that crosslinked reaction product is used for for example coating with lacquer effectively, tackiness agent, filler, priming paint and sealing agent product etc. (hereafter is coating and tackiness agent, or coating and adhesive product).
The formation of the unsaturated by product of non-volatile ethylenic can cause crosslinked reaction product uncomfortable as coating and adhesive product in the metathesis polymerization reaction.Specifically, in coating and tackiness agent, exist the unsaturated by product of this non-volatile ethylenic can hinder its drying (that is, keeping viscosity), can reduce or suppress its bonding or adhesive property, and can reduce its physics and/or mechanical property usually.
Be appreciated that the unsaturated by product of given ethylenic be volatile or nonvolatile depend on when estimating this performance residing pressure and temperature both.In this article, term " nonvolatile " and " volatile " they are not the absolute performances that is used to refer to the given unsaturated by product of ethylenic, but as considering that crosslinked polymkeric substance is as the actual guidance aspect the suitability of coating or tackiness agent.Therefore, these realize not having basically the metathesis polymerization reaction of the unsaturated by product of nonvolatile ethylenic that the suitable crosslinked polymkeric substance of making coating or tackiness agent can be provided.In this article, " there is not " ordinary representation basically less than 15 weight %, preferably, be more preferably the unsaturated by product of nonvolatile ethylenic, to react the total mass of the unsaturated by product of ethylenic that produces by metathesis polymerization less than 5 weight % less than 10 weight %.
Only reference point easily in the description as coating and tackiness agent, those skilled in the art may consider that the unsaturated by product of ethylenic is " nonvolatile ", if they under atmospheric pressure are not evaporated from coating or tackiness agent, described coating or tackiness agent comprise according to the present invention (1) at room temperature (about 15-35 ℃), in 24 hours, (2) at about 150 ℃, in about 10 minutes, perhaps (3) are at about 230 ℃, the crosslinked polymkeric substance that in about 30 seconds, (that is, is used to use the general drying mode of these products) and forms.
Perhaps, only reference point easily in the description as coating and tackiness agent surpasses about 12 carbon atoms if they comprise, and those skilled in the art just think that the unsaturated by product of ethylenic is " nonvolatile ".In other words, the unsaturated by product of described ethylenic should contain about 12 of 2-, is more preferably about 9 carbon atoms of 2-.
Therefore, the present invention also provides a kind of method that is suitable for the crosslinked polymkeric substance of making coating or a tackiness agent or their part for preparing, this method comprises by the many unsaturated monomers of metathesis polymerization reactive polymeric branching, wherein, the many unsaturated monomers of described branching comprise and can carry out the acyclic ethylenic unsaturated group of polymeric by metathesis reaction, make this metathesis polymerization can produce crosslinked polymkeric substance.
Significant advantage provided by the invention is that described crosslinked polymkeric substance can be prepared by the monomer that difference is arranged.Specifically, employed monomer only needs to contain the comparatively acyclic ethylenic unsaturated group of inert.Therefore, these monomers have littler toxicity than the monomer that those are used for preparing conventional crosslinked polymkeric substance usually, and also are difficult for making spontaneous crosslinked too early generation usually.In addition, suitable monomers can be provided by more cheap continuable resource such as natural oil.
When preparation crosslinked polymkeric substance of the present invention, can preferentially use the many unsaturated monomers of branching that contain end or the acyclic ethylenic unsaturated group of proximal end.By using these monomers, the formation meeting of the unsaturated by product of non-volatile ethylenic advantageously reduces, even can't avoid basically.Term " end or proximal end " is meant and can be positioned at organic moiety by described acyclic ethylenic unsaturated group (that is) end, vinyl is perhaps apart from 6 atoms of this part, preferably in 4 atoms.For example, described unsaturated group can be positioned in 6 carbon atoms of end of R of expression organic moiety, that is, and and R-C=C-C-C-C-C, R-C-C=C-C-C-C, R-C-C-C=C-C-C, R-C-C-C-C=C-C or R-C-C-C-C-C=C.
The many unsaturated monomers of branching that contain the acyclic ethylenic unsaturated group of end or proximal end can prepare by the means of any appropriate.But use cross metathesis to react preparing these monomers discoveries is especially easily.
Therefore, the present invention also provides the method for preparing crosslinked polymkeric substance, and this method comprises:
1) by making the compound and the lower molecular weight ethylenically unsaturated compounds that comprise one or more acyclic ethylenic unsaturated groups carry out the cross metathesis reaction, the compound that comprises one or more ends or the acyclic ethylenic unsaturated group of proximal end with generation, prepare the many unsaturated monomers of branching, the acyclic ethylenic unsaturated group of described end or proximal end with end or the acyclic ethylenic unsaturated group of proximal end
(a) can be used as the many unsaturated monomers of branching, and/or
(b) react so that the compound that can be used as the many unsaturated monomers of described branching to be provided with one or more other compounds; And
2) react the many unsaturated monomers of polymerization branching by metathesis polymerization, so that crosslinked polymkeric substance to be provided.
By using this cross metathesis response path, the many unsaturated monomers of branching that derive from cheap natural oil can advantageously be used for preparing unique crosslinkable coating and tackiness agent.It should be noted that this method makes that many so-called moist or semiarid natural oils (up to the present they be not suitable for coating and tackiness agent) are available at present.For example, single unsaturated triglyceride (that is the two keys of in each lipid acid arm of described tri-glyceride) can easily be used for preparing crosslinkable coating and tackiness agent.
Therefore, the present invention also provides coating (as lacquer) or adhesive product, described product comprises the many unsaturated monomers of branching, and the many unsaturated monomers of this branching contain and can carry out the acyclic ethylenic unsaturated group that polymerization forms crosslinked polymkeric substance by metathesis reaction, and olefin metathesis catalyst.
Others of the present invention are described below.
Embodiment
Except as otherwise noted, term used herein " acyclic ", together with statement as " diene monomers ", " ethylenic unsaturated group " or " ethylenic degree of unsaturation " or similarly statement, be to be used for representing group or monomeric unsaturated characteristic, rather than contain the monomer of this group or any others of part.Therefore, the part that contains " acyclic " ethylenic unsaturated group also can comprise cyclic group, but the ethylenic unsaturated group itself is no ring property, because it is not included in the ring texture.Under the situation of " acyclic " diene monomers, having only the ethylenic unsaturated group need be no ring property.
Come polymerization acyclic dienes monomer normally to know by transposition, and be generally known as ADMET (acyclic dienes transposition) polymerization.As all metathesis reactions, the ADMET polymerization comprises the reaction of transition metal alkylidene complex (being called olefin metathesis catalyst more at large) and acyclic ethylenic unsaturated group.Say on the principle, come the growth polymers chain to be considered to comprise the formation of two metal ring butane intermediate materials by the ADMET polymerization, and polymer chain is got rid of in each growth steps from active metal substance.Described spread step also comprises the unsaturated byproduct of reaction of ethylenic, the release of preferably volatile molecule such as ethene, and it need be removed from reaction environment to promote polymerization.
Itself can provide the polymkeric substance with the unsaturated main chain of line style the ADMET polyreaction.Studies show that the unsaturated characteristic of these polymkeric substance can be used in the side reaction so that crosslinked site to be provided.Specifically, the polymkeric substance that derives from the ADMET polyreaction is carried out conventional heat, ultraviolet and chemical modification process, with provide crosslinked polymer architecture (polymer (Macromolecules), 1992,25,2049-2052).
Have been found that the metathesis reaction path can be used to the effective and crosslinked polymkeric substance of the direct preparation of mode efficiently.
According to the present invention, can prepare crosslinked polymkeric substance by the many unsaturated monomers of polymerization branching.The many unsaturated monomers of this branching have atom or the nuclear that connects at least three parts at least one its usually, and at least three in them contain acyclic ethylenic unsaturated group.Described atom or endorse has and surpasses three parts and connect thereon, and surpasses three part and can comprise acyclic ethylenic degree of unsaturation.
In order more clearly to describe the described expressed implication of the many unsaturated monomers of branching with " atom or nuclear of connecting at least three parts on it ", this monomer can be expressed as easily and comprise following overall texture unit (I) at least:
BR
1R
2R
3 (I)
In the formula, B represents atom or nuclear, and various piece R
1, R
2And R
3, can be identical or different, comprising at least one can carry out the acyclic ethylenic unsaturated group of polymeric by metathesis reaction.
Described atom or nuclear (B) must have at least three connections part thereon, thereby can be considered as branch point or contact very simply.Being used for the many unsaturated monomers of branching of the present invention can have above such branch point or contact.In this case, can provide other branch point or contact by other atom or the nuclear that exists in the one or more parts that are connected in atom in the overall texture unit (I) or nuclear (B).Therefore, the many unsaturated monomers of described branching can comprise atom and the nuclear that branch point or contact are provided.
Wherein, the B in overall texture unit (I) is an atom, and it is C, Si or N normally.At this atom is under the situation of C or Si, and the branching atom can have the 4th connection part thereon, and this part also can contain at least one can carry out the acyclic ethylenic unsaturated group of polymeric by metathesis reaction.
The term " nuclear " that uses with the many unsaturated monomers of branching is meant the molecular structure that connects at least three parts on it in this article.For example, this is endorsed being ring-type aromatics or non-aromatic structure, and those as being provided by benzene or cyclohexane ring, their condensed derivative perhaps can be the set of these rings of being coupled together by alkyl.Described nuclear also can be oligomeric or paradigmatic structure.With B wherein is that the overall texture unit (I) of atom is different, is under the situation of " nuclear " at B, and containing at least one quantity that can be connected the molecule of the acyclic ethylenic unsaturated group on the nuclear can be much larger than 4.
As mentioned above, the many unsaturated monomers of described branching comprise at least three parts that are connected on atom or the nuclear usually, and various piece contains at least one can carry out the acyclic ethylenic unsaturated group of polymeric by metathesis reaction.By having the ethylenic unsaturated group of structure in this way, described monomer can advantageously come polymerization by metathesis reaction, so that crosslinked polymkeric substance directly to be provided.On the contrary, the ADMET polyreaction polymerization acyclic dienes monomer itself by routine can provide the polymkeric substance with linear main chain.
When acyclic ethylenic unsaturated group is called as " can carry out polymerization by metathesis reaction ", during perhaps with reference to " by transposition mediation (mediated) path " generation crosslinking reaction, these descriptions are used for representing that described monomeric acyclic ethylenic unsaturated group can react with metathesis catalyst in the process that forms crosslinked polymer architecture, perhaps do not react with metathesis catalyst.
It will be understood to those of skill in the art that to influence given acyclic ethylenic unsaturated group carries out polymeric susceptibility by metathesis reaction factor.For example, the part that contains acyclic ethylenic unsaturated group can be given and be influenced reactive space and/or the electronic action of unsaturated group to metathesis catalyst.In addition, as mentioned above, in order to promote metathesis reaction, the unsaturated by product of the ethylenic of reaction (itself deriving from the polymeric monomer) should be that volatility is enough, makes it to remove from reaction medium.
Usually, acyclic ethylenic unsaturated group can strengthen by near the space degree of crowding the reduction unsaturated group carry out polymeric susceptibility by metathesis reaction.Therefore, the ethylenic unsaturated group that advantageously is included in each at least three parts that are connected in atom or group is end or proximal end ethylenic unsaturated group, and can be the acyclic ethylenic unsaturated group of unsubstituted end or proximal end.
In order to reduce (if unescapable basically words) formation of the unsaturated by product of unfavorable non-volatile ethylenic in the crosslinking reaction process, but all basically ethylenic unsaturated groups are terminal or subterminal acyclic ethylenic unsaturated group in the preferred monomers, and can be unsubstituted (that is ,-CH=CH-or-CH=CH
2) end or the acyclic ethylenic unsaturated group of proximal end.
After how construct in branched monomer the effect of having understood acyclic ethylenic unsaturated group and they, those skilled in the art also will appreciate that, except acyclic unsaturated group itself, the structure of monomer remainder is compared not particularly important with composition with cross-linking process.Therefore, any organic group generally can be used as a part, as long as it can be connected on atom or the nuclear, and contains at least one and is easy to carry out the acyclic ethylenic unsaturated group of polymeric by metathesis reaction.Therefore, described part can comprise ring-type and/or branching and/or line style group, contains or is replaced by various functional groups, contains one or more heteroatomss such as N, O, S, P etc., and as mentioned above, even can comprise one or more other atom or nuclears (B) that above limit.
An advantage provided by the invention is to use the different many unsaturated monomers of arranging of branching to prepare crosslinked polymkeric substance.About aforementioned content, those skilled in the art can easily select suitable monomers.Described monomer can have lower molecular weight or can comprise oligomeric compound and polymerizable compound.For example, can use the how unsaturated prepolymer of branching to prepare crosslinked polymkeric substance.
Can be used for oligomeric or many unsaturated monomers of polymeric branching of the present invention and can have very complicated structure.For example, described monomer can be the form of polymer/oligomer, described polymer/oligomer has on it and to connect branching or the linear main chain of at least three parts as side group, and wherein at least three described side groups contain at least one separately and can carry out the acyclic ethylenic unsaturated group of polymeric by metathesis reaction.In the practice, this polymer/oligomer main chain can contain many these side groups, for example above 20.
The many unsaturated monomers of the branching of polymeric/oligomeric can use conventional polymerization technique such as radical polymerization, polycondensation and metathesis polymerization technology to prepare.
This method can use the monomer that the side group that contains the unsaturated characteristic that is necessary is provided when polymerization to prepare the many unsaturated monomers of branching of polymeric/oligomeric.In this case, the aggregation scheme of use should make side group keep necessary little saturation characteristic.
Another kind method can be used to prepare polymer/oligomer, and this polymer/oligomer has can react the reactive functional groups that the side group with necessary unsaturated characteristic is provided subsequently.For example, the styrene maleic anhydride multipolymer can prepare by conventional methods, reacts the side group that has necessary unsaturated characteristic to provide with reagent such as undecylenic alcohol subsequently.
In two kinds of methods of above direct description, be connected in the change of the monomeric ratio that the number of the side group of main polymer chain can be by being used for preparing polymer/oligomer and advantageously change.
The many unsaturated monomers that are used for branching of the present invention also can react direct or indirect preparation by cross metathesis.For example, for the many unsaturated monomers of branching that contain end or the acyclic ethylenic unsaturated group of proximal end are provided, the compound that comprises one or more acyclic ethylenic unsaturated groups can carry out the cross metathesis reaction with low-molecular-weight ethylenically unsaturated compounds.These compounds do not comprise the acyclic ethylenic unsaturated group of three or more end or proximal end usually.
The compound that comprises one or more acyclic ethylenic unsaturated groups can be the polyunsaturated compounds that has on it branching of the atom that connects at least three parts or nuclear, at least three atoms or nuclear contain one or more acyclic ethylenic unsaturated groups, for example natural oil.In this case, the cross metathesis product is the many unsaturated monomers that contain the branching of end or the acyclic ethylenic unsaturated group of proximal end, and can be used to prepare crosslinked polymkeric substance of the present invention.The many unsaturated monomers of the branching of gained also can with one or more other compounds or reagent react, for example be used for setting up the molecular weight (for example, in order to form prepolymer) of compound.Then, the many unsaturated monomers of this " modification " branching can be used to prepare crosslinked polymkeric substance of the present invention.
More than the concrete example of the cross metathesis reaction directly described be vegetables oil with ethene intersect-metathesis reaction following showing:
The compound that comprises one or more acyclic ethylenic unsaturated groups also can be the branching polyunsaturated compounds of above direct description, but is the form of prepolymer.For example, described compound can be the Synolac by the prepared in reaction of monoglyceride and Tetra hydro Phthalic anhydride.This resin can intersect with the lower molecular weight ethylenically unsaturated compounds-metathesis reaction, so that the Synolac that comprises end or the acyclic ethylenic unsaturated group of proximal end to be provided, the acyclic ethylenic unsaturated group of this end or proximal end can be used to prepare crosslinked polymkeric substance of the present invention subsequently.The ideal structure of this alkyd monomers is as follows:
Perhaps, intersection-metathesis reaction can be used to prepare precursor compound, and this precursor compound can form the many unsaturated monomers of branching that can be used to prepare crosslinked polymkeric substance of the present invention with the reaction of one or more compounds.For example, the compound that comprises one or more acyclic ethylenic unsaturated groups can be lipid acid or the fatty acid ester that derives from natural oil.This compound can intersect with the lower molecular weight ethylenically unsaturated compounds-metathesis reaction, so that end or proximal end ethylenic unsaturated fatty acids or fatty acid ester to be provided.Then, the compound of gained can with the reaction of one or more compounds so that many unsaturated monomers of the branching that can be used to prepare crosslinked polymkeric substance of the present invention to be provided.In this case, the lipid acid or the fatty acid ester that can not otherwise be used for coating and adhesive product can be converted into the valuable resource that is used for these products.
More than the concrete example of intersection-metathesis reaction of directly describing be fatty acid ester and the intersecting-metathesis reaction of ethene, as follows:
It will be understood to those of skill in the art that above-mentioned intersection-metathesis reaction also produces the unsaturated byproduct of reaction of ethylenic.But, different with the unsaturated byproduct of reaction of ethylenic that can make in the forming process of crosslinked polymkeric substance, required end that produces in described intersection-metathesis reaction process or proximal end ethylenically unsaturated compounds and the unsaturated byproduct of reaction of ethylenic can easily be separated from each other usually.
" natural oil " is meant and is commonly referred to as vegetables oil, even the oil of fish oil.These oil must comprise at least a ethylenic unsaturated group, and generally include tri-glyceride.The example of suitable natural oil includes, but are not limited to: rapeseed oil, soybean oil, oleum lini or linseed oil, tung oil, Viscotrol C and their combination.
Deriving from these oily unsaturated fatty acidss and fatty acid ester also can be used among the present invention.
" lower molecular weight ethylenically unsaturated compounds " in the description of relevant intersection-metathesis reaction is meant C
2-C
6Ethylenically unsaturated compounds.
Use the intersection-metathesis reaction of lower molecular weight simple chain alkene to study for many years.In the simple chain alkene that in these intersection-metathesis reactions, uses, be concerned by people most as the ethene that uses in the above-mentioned reaction.Comprise the so-called vinyl alcohol decomposition reaction of intersection-metathesis reaction of ethene.
Although a large amount of research to be used to studying described vinyl alcohol decomposition reaction, still exists many and uses this prepared terminal unsaturation compound, specifically is the relevant problem of terminal unsaturation carbonyl compound.These problems comprise the higher catalyst cupport of transformation efficiency and poor selectivity, needs, long reaction time and to some restrictions of feed type.
Up to the present, prove that a great problem relevant with the vinyl alcohol decomposition reaction that is difficult to overcome is to have produced the methylene radical intermediate in catalytic cycle.Ruthenium methylene radical complex compound has demonstrated has lower initial rate in olefin metathesis reactions.For the reaction that has the methylene radical intermediate, can realize the metathesis activity that continues by elevated temperature.But this method has also increased the speed of catalyst decomposes, cause need be higher catalyst cupport.
Another problem relevant with the vinyl alcohol decomposition reaction be reaction product (that is, terminal olefin) and ethene can with the inside alkene competition that exists in the parent material, to be bonded on the metathesis catalyst.This causes long reaction time, and influential to catalyst cupport, because the obvious decomposition of catalyzer can take place in reaction process.
As mentioned above, the type to the feed that can be used for the vinyl alcohol decomposition reaction has some restrictions.For example, the natural oil that contains conjugated polyunsaturated fatty acid such as the tung oil poor conversion in the vinyl alcohol decomposition reaction usually.This problem also can spread to not other polyunsaturated oil of conjugated.For example, ruthenium base olefin metathesis catalyst has the trend of catalyzed alkene isomerization reaction (except that olefin metathesis reactions).Therefore, generally in how unsaturated natural oil, find 1, the 4-diene can be in isomerization in the presence of the metathesis catalyst providing conjugated alkene, thereby produce problem same as described above.
Therefore, still need to provide another kind to be used to prepare the method for the acyclic unsaturated compound that can overcome or be reduced by at least some shortcomings relevant with aforementioned vinyl alcohol decomposition reaction.
The present invention also provides a kind of method for preparing proximal end ethylenic beta-unsaturated carbonyl compounds, and this method comprises: the carbonyl compound that comprises acyclic ethylenic unsaturated group and pure basically 2-butylene are intersected-metathesis reaction.
Have been found that pure basically 2-butylene can be effectively and be used to prepare proximal end ethylenic beta-unsaturated carbonyl compounds efficiently.This 2-butylene can be a cis or trans, perhaps their combination.Having reported in the cross metathesis reaction uses 2-butylene to produce the ethylenic beta-unsaturated carbonyl compounds.But the productive rate of these reactions is low especially.Do not want to be limited by theory, it is believed that the commercial sources of 2-butylene comprises the impurity that destroys the olefin metathesis catalyst (for example, ruthenium base metathesis catalyst) that uses in these reactions of capacity.These impurity it is believed that and comprise 1,3-butadiene at least, a kind of poison of acyclic metathesis reaction.Therefore, it is invalid so far that the cross metathesis of use 2-butylene (that is, butenol decomposes) is reacted to, invalid in practice.
By using pure basically 2-butylene, intersections-metathesis reaction can advantageously carry out at present, and its production turnover number (TON) is greater than about 5,000, preferably greater than about 10,000, is more preferably greater than about 20,000, preferably up to 90,000 or higher.
" pure basically " 2-butylene is meant that 2-butylene goes up free from foreign meter to guarantee realizing that turnover number is greater than about 5,000 substantially.Usually, impurity should exist with the amount that is no more than about 0.1mol%, in 2-butylene.
The use of 2-butylene it is believed that also advantageously have been avoided in the catalytic cycle process forming the methylene radical intermediate product, thus avoided with the vinyl alcohol decomposition reaction in the relevant problem of methylene radical intermediate product.Using another advantage of 2-butylene is as inner ethylenically unsaturated compounds, compares with ethene, and itself and unreacted ethylenic beta-unsaturated carbonyl compounds are that the degree of contention that is bonded on the catalyzer to be done is less.
The transformation efficiency of butenol decomposition reaction and selectivity can be determined by the ratio of 2-butylene and ethylenic beta-unsaturated carbonyl compounds.In order to reach high selectivity and transformation efficiency, should use and compare excessive a lot of 2-butylene with the ethylenic beta-unsaturated carbonyl compounds.This reaction can perhaps not have other solvent to exist down, and preferably carry out under high temperature (greater than 1 ℃) and high pressure (greater than 1 normal atmosphere) or low temperature (≤1 ℃) and normal atmosphere in the presence of other solvent.
It will be understood to those of skill in the art that these butenol decomposition reactions will provide proximal end ethylenic beta-unsaturated carbonyl compounds, wherein, described ethylenic unsaturated group is between second atom of side group and the 3rd atom.In other words, described ethylenic unsaturated group will be penult terminal olefinic link formula unsaturated group (that is, R-C-C-C-C=C-C).
Butenol decomposition reaction of the present invention can use the different ethylenic beta-unsaturated carbonyl compounds of arranging to carry out easily." ethylenic beta-unsaturated carbonyl compounds " is meant the ethylenically unsaturated compounds that comprises one or more carbonyl functional groups such as ester, acid amides, ketone, aldehyde or carboxylic acid.About aforementioned content, those skilled in the art can easily select to be used for the suitable ethylenic beta-unsaturated carbonyl compounds of this purpose.
Lipid acid or fatty acid ester that butenol decomposition reaction of the present invention can be used unsaturated natural oil or derive from it carry out easily, with preparation proximal end ethylenic beta-unsaturated carbonyl compounds.Described butenol decomposition reaction is particularly useful for preparing the many unsaturated monomers of crosslinkable branching of the present invention.For example, described butenol decomposition reaction can be used to preparation and prepares the many unsaturated monomers of branching by linseed oil, and is as follows:
The method of the polymkeric substance that preparation of the present invention is crosslinked can be carried out advantageously in many ways under various conditions.This species diversity partly comes from its ability that many unsaturated monomers of branching that are the liquid or solid form are provided, and also comes from it and selects monomer to make it can at room temperature pass through metathesis reaction polymeric ability.
In order to accelerate crosslinked speed and to make closely crosslinked and inert coating, under the high temperature of being everlasting (that is, up to about 240 ℃), carry out commercial run as applying body of a motor car or continuous coil with crosslinkable coating.But,, be starved of crosslinking reaction that use at room temperature can be carried out or that only use appropriate heating (that is, temperature is less than 100 ℃) just can carry out for using high temperature inconvenient or impossible temperature sensitivity base material or human consumer's application.Certainly, if apply more heat, these crosslinking reactions still can be quickened, and can be used for human consumer's application but its main advantage is these reactions.Cross-linking method of the present invention is particularly well suited to these human consumers and uses.
When carrying out method of the present invention, essential reagent can various two parts of formula systems provide.Coating of the present invention and adhesive product can described two parts of formula curable systems form provide.
Simple two parts of formula systems can comprise: comprise first part of the many unsaturated monomers of branching that are applicable to reaction of the present invention, and comprise second part of metathesis catalyst.The prescription of each part can easily mix before applying, thereby can take place crosslinked after applying by the response path of transposition mediation.
These two parts of formula systems are compared the conventional available advantage of two parts of formula systems: when mixing two parts, crosslinking reaction can be simply by postponing in the container that mixture is enclosed in sealing.By limiting mixture in this way, volatile alkene by product is limited to leave reaction environment, and can postpone metathesis reaction.But so just can prolong the time of mixed product processed and applied.
According to the character of monomer and catalyzer, crosslinked can at room temperature carrying out, it is crosslinked to promote perhaps may to need to apply heat to two parts of formula preparations of blended.Need apply heat to promote that crosslinked example is that described monomer provides with solid form.In solid form, described monomer is powdered easily, and uses conventional powder coated to be applied on the base material.Then, described catalyzer can use such as the technology of spraying and be applied on the monomer.Perhaps, because reactive limited between catalyzer and solid monomer, catalyzer can combine with pulverous monomer before putting on the base material.Crosslinked in order to promote, catalyzer/monomer is in conjunction with the available method of knowing such as infrared (IR) radiation heating.Under these conditions, apply enough heats usually to cause the monomer fusing.
As another kind of two parts of formula systems, first part can comprise many unsaturated monomers of branching and acyclic dienes monomer, and second part can comprise metathesis catalyst.These two parts of formula systems can the mode identical with above-mentioned system be used basically.But, existing under the monomeric situation of acyclic dienes, it provides sizable turndown ratio, thereby can regulate the The Nomenclature Composition and Structure of Complexes of the crosslinked polymkeric substance of gained.Cross-linking density that it should be noted that the crosslinked polymkeric substance of gained can easily be regulated.For example, by providing first part, can reduce the cross-linking density of the crosslinked polymkeric substance of gained with diene monomers.On the contrary, by providing first part that has seldom or do not have diene monomers, can increase the cross-linking density of the crosslinked polymkeric substance of gained.
Therefore, method of the present invention also can comprise by metathesis polymerization reactive polymeric acyclic dienes monomer.
The cross-linking density that it shall yet further be noted that the crosslinked polymkeric substance that the present invention prepares also can change by the character that changes the many unsaturated monomers of branching.In this case, more get close to mutually by making monomeric acyclic unsaturated group, the cross-linking density of the crosslinked polymkeric substance of gained is usually greater than the bigger at interval situation of unsaturated group.
Therefore, by the character and the use acyclic dienes monomer that change the many unsaturated monomers of branching, this method provides sizable turndown ratio, thereby can regulate the The Nomenclature Composition and Structure of Complexes of the crosslinked polymkeric substance of gained.
When being used in combination with the many unsaturated monomers of branching when preparing crosslinked polymkeric substance, the acyclic dienes monomer also should react with metathesis catalyst in cross-linking process.Therefore, described diene monomers must have at least two energy and carries out polymeric ethylenic unsaturated group by metathesis reaction.Suitable acyclic dienes monomer is normally known, and can easily obtain.Specifically, those are applicable to that conventional ADMET polymeric monomer can be used as the acyclic dienes monomer.
The acyclic dienes monomer that is used in combination with the many unsaturated monomers of branching can be the form of liquid or solid.When the acyclic many unsaturated monomers of branching and diene monomers all were solid form, they can be by for example extruding melting mixing easily, and powdered is to be used for above-mentioned powder coating method then.
Another kind of two parts of formula systems also comprise: comprise first part of the many unsaturated monomers of branching that are applicable to reaction of the present invention, and comprise by the polymkeric substance of ADMET polymerization preparation second part.In this case, importantly the polymkeric substance that makes of ADMET has kept active catalyst component." kept active catalyst component " and be meant that the polymeric reaction product of ADMET polyreaction is attended by the metathesis catalyst that can promote further polyreaction.
In these two parts of concrete formula systems, the prescription of each part can mix before applying, thereby can carry out crosslinked after applying by the response path of transposition mediation.But different with aforementioned two parts of formula systems, catalyst component is to provide by the polymkeric substance that ADMET makes.In this case, described catalyzer keeps dormant state effectively, until the component combination of each part.This one or two part of formula system can be used with the described substantially the same mode of above-mentioned system.For example, the polymkeric substance that monomer and ADMET make can provide by solid form, and applies by powder coating process.Perhaps, the polymkeric substance that monomer and/or ADMET make can be with suitable solvent solvation, so that the system of liquid curable to be provided.
The method of the polymkeric substance that preparation of the present invention is crosslinked can be used as mass polymerization or carries out in organic solvent.By providing as low-viscosity (mobile) liquid or be the many unsaturated monomers of branching of solid form, above-mentioned two parts of formula systems can use seldom or not with an organic solvent (if not having organic solvent) prepare.In this system, use seldom or not with an organic solvent (if not having organic solvent) be particularly advantageous because all the admissible volatility organic content (VOC) of coating and adhesive product is had legal requirements in many countries.
The method of cross-linked polymer of the present invention can easily apply so that effective coating and tackiness agent to be provided.Coating of the present invention and tackiness agent comprise: the many unsaturated monomers of branching, and it contains and can carry out polymerization to form the acyclic ethylenic unsaturated group of crosslinked polymkeric substance by metathesis reaction; And olefin metathesis catalyst.It will be appreciated by those skilled in the art that other suitable recipe ingredient also can be included in described coating and the tackiness agent.The example of these recipe ingredients includes, but are not limited to: thickening material, anti-mycotic agent, UV absorption agent, supplement, pigment and tinting material.
The solidified product that is formed by coating of the present invention and tackiness agent can comprise the polymer materials that does not form by the transposition crosslinking reaction.Therefore, described coating and tackiness agent can be mixed with and can't help that metathesis polymerization reaction forms with other or do not participate in the polymkeric substance and/or the monomeric blend of metathesis polymerization reaction.
The significant advantage of coating of the present invention and tackiness agent is that the crosslinked polymer architecture of product does not form by autoxidation.As described above, the autoxidation process can continue the long time (that is, after coating or tackiness agent drying), and can cause the decline of the physicals of coating or tackiness agent.For example, in oil base coating, the degraded of crosslinked polymkeric substance can cause the exposure that becomes of the granules of pigments on the coating surface, causes being called the problem of chalkification.Because have or form the conjugation unsaturated group of remnants in the polymkeric substance that forms paint film, oil base coating also is easy to flavescence.
With the progressively different in kind of progress of autoxidation, the response path of the transposition of using in the cross-linking method of the present invention mediation took place in the limited time period that spreads over equably in the composition.In addition, the feed monomer that is used for the transposition crosslinking reaction is difficult for crosslinked polymeric articles at gained and contains or cause remaining conjugation unsaturated group.Therefore, compare with the product that ordinary method forms, crosslinked polymeric articles of the present invention keeps its physicals usually, is difficult for the passing of time and flavescence.
The present invention includes the use olefin metathesis catalyst.Those skilled in the art can easily select and obtain appropriate catalyst to implement the present invention.The example of suitable olefin metathesis catalyst comprises, but be not limited to: Ge Busi (Grubbs) catalyst I generation or benzylidene-two (tricyclohexyl phosphine) dichloro ruthenium, Ge Busi catalyst I I generation or benzylidene [1,3-two (2,4, the 6-trimethylphenyl)-and the inferior imidazolidyl (imidazolidinylidene) of 2-] dichloro (tricyclohexyl phosphine) ruthenium, and Ha Weida-Ge Busi catalyst I I generation or 1,3-two-(2,4, the 6-trimethylphenyl)-the inferior imidazolidyl of 2-) dichloro (neighbour-isopropoxy benzene methylene) ruthenium.
For butenol decomposition reaction and crosslinked with the butenol degradation production, preferred Ge Busi catalyst I I generation and Ha Weida-Ge Busi catalyst I I generation.
Olefin metathesis catalyst can make it can promote the form of polymeric any appropriate to provide.For example, this catalyzer can maybe can be a solid bond with suitable carriers material such as solvent, and forms tablet.Be appreciated that any this solid support material should with other component compatibility of described curable system.
Embodiment
Embodiment 1
The butenol of triolein decomposes
Emptying is equipped with Qi Lunke (schlenk) pipe of magnetic stirring bar, is full of argon gas then, and places the methanol bath that is cooled to-5 ℃.With cis-2-butene (1.30g, 23.2mmol) and triolein (0.75mL 7.7mmol) fills pipe.Will (0.145 μ g, 2.32nmol) solution adds in the pipe, and uses magnetic stirring bar to stir the mixture 256 minutes for catalyzer at Ha Weida-Ge Busi (Hoveyda-Grubbs) II in the methylene dichloride (10 μ L).Then, finish reaction by adding ethyl vinyl ether (500 μ L).Method by routine is carried out transesterify with methyl alcohol to the product sample, and analyzes ester exchange offspring with vapor-phase chromatography (GC), show the oleic acid chain to the transformation efficiency of 9-undecylenic acid (undecenoic) chain greater than 90%.This transformation efficiency is equivalent to TON for catalyzer greater than 90,000.
Embodiment 2
Carry out the butenol decomposition of Witconol 2301 with the 2-butylene of different purity
Emptying is equipped with the Qi Lunke pipe of magnetic stirring bar, is full of argon gas then, and places the methanol bath that is cooled to-5 ℃.Use derives from the different sample of 2-butylene specimen preparation of different sources:
Sample A (contrast): cis+trans 2-butylene (containing 2.6% 1,3-butadiene)
Sample B: cis-2-butene (not containing 1,3-butadiene)
Sample C (contrast): the cis 2-butylene (not containing 1,3-butadiene) that is doped with 2% divinyl
The amount of the 2-butylene that adds under the various situations identical (1.30g, 23.2mmol).With independent distillatory Witconol 2301 (1.45mg, 4.88mmol) and the Ha Weida-Ge Busi II in methylene dichloride (10 μ L) (0.145 μ g, 2.32nmol) solution adds in the pipe, and uses magnetic stirring bar to stir the mixture 256 minutes for catalyzer.Then, finish reaction by adding ethyl vinyl ether (500 μ L).Come analytical sample with GC and oleic acid chain in contrast to the transformation efficiency of 9-undecylenic acid chain.
The result:
| Sample A | The transformation efficiency of trace＜＜1% |
| Sample B | ＞90% transformation efficiency |
| Sample C | The transformation efficiency of trace＜＜1% |
Embodiment 3
The butenol of Witconol 2301 decomposes (butenolysis)
The stainless steel autoclave that will have glass liner is equipped with magnetic stirring bar, and (0.34g is 1.1mmol) with II Dai Gebusi catalyzer (9.3mg, 0.11 μ mol) to fill ethyl oleate.Use the argon cleaning autoclave.The emptying autoclave, cis-2-butene is forced into the pressure of 15psi then.Under agitation spend the night in 60 ℃ of heating high-pressure stills.Then relief pressure adds ethylene vinyl base ether (50 μ L) in the reaction mixture.With methyl alcohol the product sample is carried out transesterify by ordinary method, and analyzes ester exchange offspring with GC, show the oleic acid chain to the transformation efficiency of 9-undecylenic acid chain greater than 85%.
Embodiment 4
The butenol of rapeseed oil decomposes
To be equipped with the 2L round-bottomed flask of magnetic stirring bar to be immersed in the methanol bath.(80.97g) fills flask with rapeseed oil, emptying then, and stirred 1 hour fast with oil.Then, be full of flask, and methanol bath be cooled to-7 ℃ with argon gas.Then, (204.5g 3.65mol) fills flask with cis+trans-2-butylene.To add in the flask for catalyzer (11.4mg, 0.18 μ mol) solution at the Ha Weida in the methylene dichloride (1mL)-Ge Busi II, and use magnetic stirring bar to stir the mixture 64 minutes.Then, tricyclohexyl phosphine (0.15g) in mixture.The temperature of bathing is elevated to about 40 ℃ lentamente, and collects volatile matter by distillation.With methyl alcohol little product sample is carried out transesterify by ordinary method, and analyzes ester exchange offspring with GC, show the unsaturated fatty acids chain to the transformation efficiency of 9-undecylenic acid chain greater than 95%.
Embodiment 5
The butenol of soya-based Synolac decomposes
The 2L round-bottomed flask that is equipped with magnetic stirring bar is immersed in the methanol bath that is cooled to-10 ℃.The emptying flask, and be full of flask with argon gas.Be used in the degassing of the soya-based Synolac (90g) in the methylene dichloride (100mL) solution, cis+trans-2-butylene (166g, 2.96mol) and Ha Weida-Ge Busi II (0.10g 16.0mmol) fills flask for catalyzer.Use magnetic stirring bar to stir the mixture about 90 minutes.Then, (0.10g 16.0mmol), continues to stir 60 minutes again for catalyzer to add Victor, additional Kazakhstan-Ge Busi II in reaction.Tricyclohexyl phosphine in mixture (0.15g).The temperature of bathing is elevated to room temperature lentamente, and collects volatile matter by distillation.Spend the night by rest solution with the air foaming.With methyl alcohol little product sample is carried out transesterify by ordinary method, and analyzes ester exchange offspring with GC, show the unsaturated fatty acids chain to the transformation efficiency of 9-undecylenic acid chain greater than 90%.By under high vacuum in 150 ℃ of heating products 15 minutes, from product, remove other volatile compound.
Embodiment 6
Two 11-10-carbon enoic acids 2,2-two ((11-10-carbene acyloxy) methyl) propane-1, the preparation of 3-diester
With TriMethylolPropane(TMP) (2.73g, 20.34mmol), undecylenic acid (undecnylenic acid) (15.0g, 81.39mmol, 4 equivalents) and DMAP (0.99g, 8.136mmol, 0.4 equivalent) be dissolved in the tetrahydrofuran (THF) (150ml), and mixture is cooled to 0 ℃.In mixture, drip the DCC (16.77g, 81.39mmol, 4 equivalents) in tetrahydrofuran (THF) (45ml), and kept 30 minutes, be heated to 20 ℃ and stirred 3 days then at 0 ℃.Filtering mixt (to remove N, the N-dicyclohexylurea (DCU)) is with disgorging.Depress the remaining transparent liquid of reduction at branch.Absorption of residual excess in ether cleans with yellow soda ash (10% aqueous solution), salt solution, uses dried over mgso, filters, and depresses reduction at branch.By flash chromatography (vinyl acetic monomer/hexane: 5/95) purified feed stock, to obtain 9.55g (74%) hentriaconta--10-carbon enoic acid ethane-1,1,1-three esters are as yellow oil; IR (film) 3467,3076,2922,2855,2120,1746,1640,1464,1417,1386,1355,1236,1158,1116,1056,994,909,783,724cm
-1 1H NMR (CDCl
3): δ=5.90-5.72 (m, 3H), 5.04-4.87 (m, 6H), 4.00 (s, 6H), 2.28 (t, 6H, J=2.26Hz), 2.07-1.99 (m, 6H), 1.62-1.55 (m, 6H), 1.52-1.43 (m, 2H), 1.42-1.34 (m, 30H), 0.88 (t, 3H, J=2.12Hz);
13C NMR (CDCl
3): δ=173.2,138.9,114.0,63.6,40.5,34.1,33.6,29.2,29.1,29.0,28.9,28.7,24.8,23.0,7.2; MS-ESI m/z 655.6 (M+Na
+).Analyze, calculate C
39H
68O
6: C, 74.00; H, 10.83.Find: C, 73.98; H, 11.01.
Embodiment 7
Two 11-10-carbon enoic acid 2-ethyl-2-((11-10-carbene acyloxy) methyl) propane-1, the preparation of 3-diester
With tetramethylolmethane (pentaerythrilol) (2.94g, 21.59mmol), undecylenic acid (20.0g, 108.53mmol, 5 equivalents) and DMAP (1.32g, 10.85mmol, 0.5 equivalent) be dissolved among the THF (150ml), and mixture is cooled to 0 ℃.In mixture, drip the DCC (22.28g, 108.53mmol, 5 equivalents) in THF (50ml), and kept 30 minutes, be heated to 20 ℃ and stirred 3 days then at 0 ℃.Filtering mixt is depressed reduction at branch then.Absorption of residual excess in ether (200ml) cleans with yellow soda ash (10% aqueous solution), salt solution, uses dried over mgso, filters, and depresses reduction at branch.By flash chromatography (vinyl acetic monomer/hexane: 5/95) purified feed stock, to obtain 12.65g (72%) 2-ethyl-2-((11-10-carbene acyloxy) methyl) propane-1,3-two bases are as yellow oil; IR (film) 3469,3076,2926,2855,1745,1640,1466,1416, and 1389,1355,1235,1157,11 16,994,909,724cm
-1 1H NMR (CDCl
3): δ=5.86-5.72 (m, 4H), 5.01-4.89 (m, 8H), 4.10 (s, 8H, CCH
2O), and 2.31-2.26 (m, 8H), 2.06-1.99 (m, 8H), 1.63-1.53 (m, 8H), 1.42-1.22 (m, 40H);
13C NMR (CDCl
3): δ=173.1,139.0,114.1,62.1,41.83,34.0,33.7,29.2,29.1,29.0,28.9,28.8,24.8; MS-ESI m/z 801.8 (M+H)
+Analyze, calculate C
49H
84O
8: C, 73.46; H, 10.57.Find: C, 73.39; H, 10.65.
Embodiment 8
The preparation of the diester of dihydroxyphenyl propane and 10-undecylenic acid
With 2, the 2-diallyl bisphenol (1.577g, 5.11mmol) and undecene acyl chloride (3.11g, 15.34mmol, 3 equivalents) combine, and 60 ℃ of heated mixt 16 hours.In ether (50ml), absorb mixture, and (3 * 50ml) clean, and then (2 * 40ml) clean, and use anhydrous magnesium sulfate drying, filter, and depress reduction at branch with salt solution with sodium bicarbonate (saturated aqueous solution).By flash chromatography (vinyl acetic monomer/hexane: 5/95) purified feed stock, to obtain 3.11g (95%) product as light yellow oil;
1H NMR (CDCl
3): δ=7.09-7.04 (m, 4H), 6.92-6.90 (m, 2H), 5.90-5.77 (m, 4H), 5.04-4.92 (m, 8H), 6.50 (d, 4H, J=6.3Hz), 2.54 (t, 4H, J=7.5Hz), 2.08-2.01 (m, 4H), 1.77-1.70 (m), 1.64 (s, 6H), and 1.43-1.32 (bs, 24H);
13C NMR (CDCl
3): δ=172.8,148.3,147.1,139.4,136.3,131.2,128.9,126.2,121.9,116.7,114.4,42.7,35.1,34.6,34.0,31.2,29.5,29.4,29.3,29.2,29.1,25.2; MS-ESI m/z (M+H)
+Analyze, calculate C
43H
60O
4: C, 80.58; H, 9.44.Find: C, 78.81; H, 9.30.
Embodiment 9
The butenol degradation production of rapeseed oil crosslinked to form film
From the butenol degradation production (for example, deriving from the product of the fs of embodiment 4) of rapeseed oil, remove the sample alkene by vacuum distilling, stay lurid oil.Should oil sample (0.46g) mix with titanium dioxide (0.29g) and grind to form uniform mixture.This mixture is placed on the slide, and be added in Ha Weida-Ge Busi II in the methylene dichloride (10 μ L) for catalyzer (15mg) solution, thorough mixing.Apply this mixture to cover the zone of 40 * 60mm.After 1 hour, find that film is solidified as solid film, mass loss is 0.025g.Find that this film is soluble in following solvent: water, methyl alcohol, acetone, vinyl acetic monomer, hexane, toluene.
Embodiment 10
Crosslinked based on the Synolac of 9-undecylenic acid to form film
With titanium dioxide (0.63g) and toluene 0.5mL the product sample (1.0g) of embodiment 5 is ground to form uniform mixture.Ha Weida-Ge Busi II is mixed in the mixture fully for catalyzer (15mg), then it is coated on the slide.After 10 minutes, film solidifies and obtains glossiness surface.This film (being soft slightly during beginning) progressively hardening in ensuing 12 hours is finally adhered to hard firm film on glass well.Find that this film is soluble in following solvent: water, methyl alcohol, acetone, vinyl acetic monomer, hexane, toluene.
Color relatively
With derive from test with the film of white pigment lacquer with derive from commercially available white pigment alkyd varnish (how happy scholar's high gloss porcelain lacquer (Dulux High Gloss Enamel)) and make comparisons.Film that rod will test with sample and commercially available prod casts on the plate of sealing complete drying film in 48 hours to use #40 to reel off raw silk from cocoons downwards.With test with the aberration between film and the commercial membrane with same with reference to comparing with white ceramic tile, and use CIE1976 colour system calculating aberration coordinate.Then, quicken the aging of sample by adopting identical plate and it being wrapped in metal tin inside, this metal tin has the lid of sealing, and the solution of ammonium hydroxide body of wherein having placed 5ml 10% makes the atmosphere in the jar saturated.Plate is exposed 48 hours under these conditions.
The result:
| ΔL | Δa | Δb | ||
| Embodiment 10 | Before ammonia exposes | -0.70 | 0.03 | 0.47 |
| After ammonia exposes | -0.35 | -0.25 | 1.33 | |
| Commercially available sample (contrast) | Before ammonia exposes | 0.10 | -0.69 | 1.77 |
| After ammonia exposes | -2.69 | -0.42 | 12.74 | |
Before being exposed to ammonia, test can clearly be confirmed by eyes at the notable difference aspect yellow (+1.30) with sample and control sample.The effect that ammonia exposes is to be known as the test that has the trend correlation connection of the flavescence of passing in time with conventional porcelain lacquer.After ammonia exposed, control sample demonstrated become significantly more yellow (+11.41).Do not have autoxidation owing to derive from the film of testing with sample, these outcome expectancies reflections are by exposing the difference that passs in time and obtain naturally.In other words, crosslinked film of the present invention expectation with the passing of time seldom or not flavescence.
Embodiment 11
Two 11-10-carbon enoic acid 2-ethyl-2-((11-10-carbene acyloxy) methyl) propane-1,3-diester crosslinked to obtain film
I Dai Gebusi catalyzer (10mg) is dissolved in the methylene dichloride of minimum volume, and with two 11-10-carbon enoic acid 2-ethyl-2-((11-10-carbene acyloxy) methyl) propane-1, the 3-diester mixes.This mixture is coated on the petri diss.After 17 hours, mixture becomes hard, elastomeric film.
In this specification sheets and appending claims, except as otherwise noted, word " comprises " and variant " contains ", is appreciated that the group that comprises described integer or step or integer or step for expression, but does not get rid of the group of any other integer or step latter integer or step.
In this specification sheets not, and should not be considered as approval or admit or the existing open source literature (perhaps deriving from its information) of suggestion or known content form the conventional, well-known general knowledge in the field that this specification sheets attempts to relate in any form a part any existing open source literature (perhaps deriving from its information) or the reference of any known content.
Claims (19)
1. method for preparing crosslinked polymkeric substance, this method comprises: react the many unsaturated monomers of polymerization branching by metathesis polymerization, wherein, the many unsaturated monomers of described branching comprise by metathesis reaction and carry out the acyclic ethylenic unsaturated group that polymeric is positioned at end or proximal end place, make this metathesis polymerization produce crosslinked polymkeric substance, and the many unsaturated monomers of described branching are natural oil or derive from natural oil.
2. the method for claim 1 is characterized in that, it also comprises by metathesis polymerization reactive polymeric acyclic dienes monomer.
3. method as claimed in claim 1 or 2 is characterized in that, described end or subterminal acyclic ethylenic unsaturated group are unsubstituted.
4. method as claimed in claim 1 or 2 is characterized in that, described natural oil is selected from rapeseed oil, soybean oil, oleum lini, linseed oil, tung oil, Viscotrol C and their combination.
5. method as claimed in claim 1 or 2 is characterized in that, the many unsaturated monomers of described branching are prepared directly or indirectly by intersection-metathesis reaction.
6. method for preparing crosslinked polymkeric substance, this method comprises:
1) preparation has the many unsaturated monomers of branching that carry out polymeric end or the acyclic ethylenic unsaturated group of proximal end by metathesis reaction, and the many unsaturated monomers of described branching are by making following compound:
(a) be natural oil or derive from natural oil, and
(b) comprise one or more acyclic ethylenic unsaturated groups,
Carry out the cross metathesis reaction with the lower molecular weight ethylenically unsaturated compounds and prepare, wherein this compound with the compound that generation comprises one or more ends or the acyclic ethylenic unsaturated group of proximal end:
(c) as the many unsaturated monomers of branching, and/or
(d) react to provide described branching many unsaturated monomers with one or more compounds; And
2) react the many unsaturated monomers of polymerization branching by metathesis polymerization, so that crosslinked polymkeric substance to be provided.
7. method as claimed in claim 6 is characterized in that, the described compound that is used for preparing comprising of the many unsaturated monomers of branching of one or more acyclic ethylenic unsaturated groups is the fatty acid ester that derives from the lipid acid of natural oil or derive from natural oil.
8. as claim 6 or 7 described methods, it is characterized in that described natural oil is selected from rapeseed oil, soybean oil, oleum lini, linseed oil, tung oil, Viscotrol C and their combination.
9. as claim 6 or 7 described methods, it is characterized in that described lower molecular weight ethylenically unsaturated compounds is pure basically 2-butylene.
10. coating or adhesive product, it comprises
1) the many unsaturated monomers of branching
(a) contain by metathesis reaction and carry out end or the proximal end acyclic ethylenic unsaturated group of polymerization to form crosslinked polymkeric substance, and
(b) be natural oil or derive from natural oil and
2) olefin metathesis catalyst.
11. coating as claimed in claim 10 or adhesive product is characterized in that, it is the form of two parts of formula curable systems, and the many unsaturated monomers of wherein said branching are provided in first part, and described olefin metathesis catalyst is provided in second part.
12. coating as claimed in claim 11 or adhesive product is characterized in that, described first part also comprises the acyclic dienes monomer.
13., it is characterized in that described second part also comprises the polymkeric substance that forms by the acyclic dienes metathesis polymerization as claim 10 or 12 described coating or adhesive products.
14., it is characterized in that described olefin metathesis catalyst is selected from Ge Busi catalyst I generation and II generation as claim 10 or 11 described coating or adhesive products.
15. method for preparing proximal end ethylenic beta-unsaturated carbonyl compounds, this method comprises: the carbonyl compound that comprises acyclic ethylenic unsaturated group and pure basically 2-butylene are intersected-metathesis reaction, wherein, described carbonyl compound is natural oil or derives from natural oil.
16. method as claimed in claim 15 is characterized in that, described carbonyl compound comprises one or more carbonyl functional groups that are selected from ester, acid amides, ketone, aldehyde, carboxylic acid and their combination.
17., it is characterized in that described intersection-metathesis reaction provides and surpasses about 10,000 production turnover number as claim 15 or 16 described methods.
18., it is characterized in that described carbonyl compound is the fatty acid ester that derives from the lipid acid of natural oil or derive from natural oil as claim 15 or 16 described methods.
19., it is characterized in that described natural oil is selected from rapeseed oil, soybean oil, oleum lini, linseed oil, tung oil, Viscotrol C and their combination as claim 15 or 16 described methods.
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| US60/695,439 | 2005-07-01 | ||
| PCT/AU2006/000930 WO2007002999A1 (en) | 2005-07-01 | 2006-06-30 | Crosslinking method |
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| CN101273077A CN101273077A (en) | 2008-09-24 |
| CN101273077B true CN101273077B (en) | 2011-06-08 |
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| US6645261B2 (en) | 2000-03-06 | 2003-11-11 | Cargill, Inc. | Triacylglycerol-based alternative to paraffin wax |
| US6503285B1 (en) | 2001-05-11 | 2003-01-07 | Cargill, Inc. | Triacylglycerol based candle wax |
| US7128766B2 (en) | 2001-09-25 | 2006-10-31 | Cargill, Incorporated | Triacylglycerol based wax compositions |
| EP1603857A4 (en) | 2003-01-13 | 2006-05-17 | Cargill Inc | Method for making industrial chemicals |
| US7192457B2 (en) | 2003-05-08 | 2007-03-20 | Cargill, Incorporated | Wax and wax-based products |
| EP2292697A1 (en) | 2005-01-10 | 2011-03-09 | Elevance Renewable Sciences, Inc. | Candle and candle wax containing metathesis and metathesis-like products |
| US8815257B2 (en) | 2006-03-07 | 2014-08-26 | Elevance Renewable Sciences, Inc. | Compositions comprising metathesized unsaturated polyol esters |
| WO2007103460A2 (en) | 2006-03-07 | 2007-09-13 | Elevance Renewable Sciences, Inc. | Colorant compositions comprising metathesized unsaturated polyol esters |
| US8344052B2 (en) | 2006-07-12 | 2013-01-01 | Elevance Renewable Sciences, Inc. | Hot melt adhesive compositions comprising metathesized unsaturated polyol ester wax |
| WO2008010961A2 (en) | 2006-07-13 | 2008-01-24 | Elevance Renewable Sciences, Inc. | Synthesis of terminal alkenes from internal alkenes and ethylene via olefin metathesis |
| WO2008103289A1 (en) | 2007-02-16 | 2008-08-28 | Elevance Renewable Sciences, Inc. | Wax compositions and methods of preparing wax compositions |
| CA2689194C (en) | 2007-05-30 | 2015-10-27 | Elevance Renewable Sciences, Inc. | Prilled waxes comprising small particles and smooth-sided compression candles made therefrom |
| WO2008157436A1 (en) | 2007-06-15 | 2008-12-24 | Elevance Renewable Sciences, Inc. | Hybrid wax compositions for use in compression molded wax articles such as candles |
| WO2011112486A1 (en) | 2010-03-10 | 2011-09-15 | Elevance Renewable Sciences, Inc. | Lipid-based wax compositions substantially free of fat bloom and methods of making |
| WO2011135029A1 (en) | 2010-04-28 | 2011-11-03 | Dsm Ip Assets B.V. | Metathesis crosslinkable coating compositions |
| WO2011143037A1 (en) | 2010-05-12 | 2011-11-17 | Elevance Renewable Sciences, Inc. | Natural oil based marking compositions and their methods of making |
| EP2590911B1 (en) | 2010-07-09 | 2014-05-14 | Elevance Renewable Sciences, Inc. | Waxes derived from metathesized natural oils and amines and methods of making |
| EP2643445B1 (en) | 2010-11-23 | 2019-01-30 | Cargill, Incorporated | Lipid-based wax compositions substantially free of fat bloom and methods of making |
| CA2841137A1 (en) | 2011-07-10 | 2013-01-17 | Elevance Renewable Sciences, Inc. | Metallic soap compositions for various applications |
| US9120896B2 (en) | 2012-09-28 | 2015-09-01 | Elevance Renewable Sciences, Inc. | Polymers containing metathesized natural oil derivatives |
| JP6744877B2 (en) * | 2016-01-28 | 2020-08-19 | 富士フイルム株式会社 | Solid electrolyte composition, solid electrolyte-containing sheet and all-solid secondary battery, and method for manufacturing solid electrolyte-containing sheet and all-solid secondary battery |
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| US6800170B2 (en) * | 2001-06-25 | 2004-10-05 | Lord Corporation | Metathesis polymerization adhesives and coatings |
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| US4545941A (en) * | 1983-06-20 | 1985-10-08 | A. E. Staley Manufacturing Company | Co-metathesis of triglycerides and ethylene |
| EP0799090B1 (en) * | 1994-12-21 | 1999-05-19 | Rwe-Dea Aktiengesellschaft Für Mineraloel Und Chemie | Aluminosilicate carrier for metathesis catalysts |
| US6962729B2 (en) * | 1998-12-11 | 2005-11-08 | Lord Corporation | Contact metathesis polymerization |
| EP1377537B1 (en) * | 2001-03-26 | 2009-04-22 | Dow Global Technologies Inc. | Metathesis of unsaturated fatty acid esters or unsaturated fatty acids with lower olefins |
| CN101172952B (en) * | 2002-04-29 | 2013-03-27 | 陶氏环球技术有限责任公司 | Integrate chemical processes for industrial utilization of seed oils |
| CN100590104C (en) * | 2002-10-24 | 2010-02-17 | 陶氏环球技术公司 | Stabilization of olefin metathesis product mixtures |
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2006
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- 2006-06-30 US US11/988,180 patent/US8211989B2/en active Active
- 2006-06-30 WO PCT/AU2006/000930 patent/WO2007002999A1/en active Application Filing
- 2006-06-30 EP EP11170379A patent/EP2366685A1/en not_active Withdrawn
- 2006-06-30 EP EP06760832A patent/EP1899398A4/en not_active Withdrawn
- 2006-06-30 CN CN2006800242292A patent/CN101273077B/en not_active Expired - Fee Related
- 2006-06-30 JP JP2008518570A patent/JP2008545021A/en not_active Withdrawn
- 2006-06-30 NZ NZ588394A patent/NZ588394A/en not_active IP Right Cessation
- 2006-06-30 CA CA002613687A patent/CA2613687A1/en not_active Abandoned
- 2006-06-30 NZ NZ565252A patent/NZ565252A/en not_active IP Right Cessation
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2007
- 2007-12-21 ZA ZA200711186A patent/ZA200711186B/en unknown
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2012
- 2012-06-01 US US13/487,084 patent/US20120238693A1/en not_active Abandoned
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4049616A (en) * | 1974-11-18 | 1977-09-20 | The Goodyear Tire & Rubber Company | Preparation of graft, block and crosslinked unsaturated polymers and copolymers by olefin metathesis |
| US6800170B2 (en) * | 2001-06-25 | 2004-10-05 | Lord Corporation | Metathesis polymerization adhesives and coatings |
Also Published As
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| US20090186976A1 (en) | 2009-07-23 |
| JP2008545021A (en) | 2008-12-11 |
| EP1899398A4 (en) | 2009-09-02 |
| AU2006265769A1 (en) | 2007-01-11 |
| EP2366685A1 (en) | 2011-09-21 |
| ZA200711186B (en) | 2009-01-28 |
| NZ588394A (en) | 2011-10-28 |
| CN101273077A (en) | 2008-09-24 |
| NZ565252A (en) | 2010-10-29 |
| WO2007002999A1 (en) | 2007-01-11 |
| US8211989B2 (en) | 2012-07-03 |
| US20120238693A1 (en) | 2012-09-20 |
| EP1899398A1 (en) | 2008-03-19 |
| AU2006265769B2 (en) | 2011-08-18 |
| CA2613687A1 (en) | 2007-01-11 |
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